Water mark defect prevention for immersion lithography

ABSTRACT

A photoresist material having a polymer that turns soluble to a base solution in response to reaction with acid. The material includes a photo-acid generator (PAG) that decomposes to form acid in response to radiation energy and a quencher capable of neutralizing acid and having a reduced mobility. The photoresist material can thereby prevent water mark defects from immersion lithography.

CROSS REFERENCES

This application claims priority from U.S. Provisional PatentApplication Ser. No. 60/722,646 filed on Sep. 30, 2005, entitled “WaterMark Defect Prevention for Immersion Lithography” and is related to thefollowing commonly-assigned U.S. Patent Applications, the entiredisclosures of which are hereby incorporated herein by reference: U.S.patent application Ser. No. 11/324,588 filed Jan. 3, 2006, which claimspriority to U.S. Patent Application Nos. 60/722,316 filed Sep. 30, 2005and 60/722,646 filed Sep. 30, 2005, having the same inventor and sameassignee as the present invention. This application is also related toU.S. patent application Ser. No. 11/384,624 filed Mar. 20, 2006, whichclaims priority to U.S. Patent Application No. 60/695,562 filed Jun. 30,2005; and U.S. patent application Ser. No. 11/427,017 filed Jun. 28,2006, which claims priority to U.S. Patent Application No. 60/705,795filed Aug. 5, 2005.

BACKGROUND

As semiconductor fabrication technologies are continually progressing tosmaller feature sizes such as 65 nanometers, 45 nanometers, and below,immersion lithography processes are being adopted. However, immersionlithography processes induce water drop residue after an exposureprocess. Such water drop residue can cause water mark defects andtherefore degrade or even cause failures during semiconductorfabrication.

What is needed is an improved immersion lithography system where thedamage caused by water mark defects are prevented and/or reduced.

BRIEF DESCRIPTION OF THE DRAWINGS

Aspects of the present disclosure are best understood from the followingdetailed description when read with the accompanying figures. It isnoted that, in accordance with the standard practice in the industry,various features are not drawn to scale. In fact, the dimensions of thevarious features may be arbitrarily increased or reduced for clarity ofdiscussion.

FIG. 1 illustrates a sectional view of one exemplary semiconductordevice 100 having a photo sensitive layer being exposed during animmersion lithography process.

FIGS. 2 and 3 illustrate sectional views of one exemplary semiconductordevice having photo sensitive layer and watermark formed thereon duringimmersion lithography processes.

FIG. 4 illustrates a schematic view of a photo sensitive layer havingchemically bonded quenchers.

FIGS. 5 a to 5 c illustrate schematic views of various embodiments of aphoto sensitive layer having a polymer and quenchers chemically bondedto the polymer.

FIG. 6 illustrates a schematic view of a photo sensitive layer havingphysically trapped quenchers.

FIGS. 7 a to 7 j illustrate schematic views of various embodiments of aphoto sensitive layer having quenchers with reduced mobility.

FIGS. 8 a to 8 b illustrate schematic views of various embodiments of aphoto sensitive layer having hydrophobic quenchers.

FIG. 9 is a flowchart of one embodiment of a method of immersionphotolithography patterning.

DETAILED DESCRIPTION

It is understood that the following disclosure provides many differentembodiments, or examples, for implementing different features of variousembodiments. Specific examples of components and arrangements aredescribed below to simplify the present disclosure. These are, ofcourse, merely examples and are not intended to be limiting. Forexample, the formation of a first feature over or on a second feature inthe description that follows may include embodiments in which the firstand second features are formed in direct contact, and may also includeembodiments in which additional features may be formed interposing thefirst and second features, such that the first and second features maynot be in direct contact. In addition, the present disclosure may repeatreference numerals and/or letters in the various examples. Thisrepetition is for the purpose of simplicity and clarity and does not initself dictate a relationship between the various embodiments and/orconfigurations discussed.

FIG. 1 provides a sectional view of a semiconductor device 100 during animmersion lithography exposing process. The semiconductor device 100 maybe a semiconductor wafer or other suitable device. In the presentembodiment, the semiconductor device 100 includes a silicon substrate110 having organic bottom anti reflecting coating (BARC), inorganicbottom anti reflective layer, etch resistance organic layer, adhesionenhancement organic layer, various doped regions, dielectric features,and multilevel interconnects. The substrate may alternatively includeother suitable semiconductor material, including Ge, SiGe, or GaAs. Thesubstrate may alternatively include a non-semiconductor material such asa glass plate for thin-film-transistor liquid crystal display (TFT-LCD)devices. The semiconductor device 100 may further include one or morematerial layers to be patterned.

The semiconductor device 100 includes a photo sensitive layer(photoresist or resist) 120. In the present embodiment, the resist layer120 has a thickness ranging between about 50 angstroms and 5000angstroms. In another embodiment, the resist layer 120 may have athickness ranging between about 500 angstroms and 2000 angstroms. Theresist layer 120 utilizes a chemical amplification (CA) resist material.The resist layer 120 includes a polymer material that turns soluble to adeveloper such as a base solution when the polymer is reacted with acid.The resist layer 120 includes a polymer material that turns insoluble toa developer such as a base solution when the polymer is reacted withacid. The resist 120 further includes a solvent filling inside thepolymer. The solvent may be partially evaporated due to a prior bakingprocess. The resist 120 also includes a photo-acid generator (PAG) 130material, with PAG molecules distributed inside the solvent and/orpolymer. When absorbing photo energy, the PAG 130 decomposes and forms asmall amount of acid. The PAG 130 may have a concentration rangingbetween about 1% and 15% wt of the resist polymer 120.

In furtherance of the present embodiment, the resist 120 also includes aquencher material 140 that distributes inside the solvent and polymer.The quencher 140 is a base type and is capable of neutralizing acid.Collectively or alternatively, the quencher may inhibit other activecomponent of the resist 120, such as inhibiting PAG and photo acid fromreaction. The quencher 140 may have a concentration ranging between 0.5%and 8% wt of the resist. The quencher 140 may alternatively have aconcentration about one fourth of the concentration of the PAG 130 byweight before the exposing process. In one example, the quencher 140includes a nitrogen atom having an unpaired electron capable ofneutralizing an acid. In an exposure processing step during an immersionphotolithographic patterning, the resist layer 120 is exposed to aradiation energy such as deep ultra-violet (DUV) through a photomask(mask or reticle) having a predefined pattern, resulting in a resistpattern that includes a plurality of unexposed regions such as unexposedfeatures 120 a and a plurality of exposed regions such as exposedfeatures 120 b. The radiation energy may include a 248 nm beam byKrypton Fluoride (KrF) excimer lasers or a 193 nm beam by Argon Fluoride(ArF) excimer lasers. The immersion lithography further includes animmersion fluid between the semiconductor device 100 and a lens of alithography system used to implement the exposure processing step. Theimmersion fluid may include de-ionized water (DI water or DIW). Thefluid may further include chemical additives such as acid, salt, orpolymer. The fluid may alternatively include other suitable fluid havingan index of refraction higher than 1.44, the index of refraction of DIW.During an exposing process, water drop residue, such as an exemplarywater drop 150, may be left on the resist layer after the exposingprocess.

In previous immersion lithography patterning processes, the water dropresidue may cause problems such as forming a watermark as illustrated insectional views of a semiconductor device 200 of FIGS. 2 and 3. A waterdrop 130 left on a photo sensitive layer 120 of the semiconductor device200 may provide a path to PAG 130 and quencher 140. The quencher 140 inunexposed resist region 120 a may diffuse into the water drop andfurther diffuse into the exposed resist region 120 b, therebyneutralizing the photo generated acid and/or reducing exposureefficiency in the exposed areas. Furthermore, the exposed PAG isdecomposed as PAG anion and acid, which is more soluble to water thanunexposed PAG. The photo generated acid may diffuse into the water dropwith additional effect such that the exposed areas of the resist 120have reduced photo generated acid. These exposed areas of the resistlayer 120 thus may have no sufficient photo generated acid to induce acascade of chemical transformation (acid amplification) after theexposing process step, and/or may not be fully soluble in developingsolution at a developing process step. Thus an unexpected T-top resistfeature (bridge profile or watermark) 120 c may be formed on the exposedregions of the resist layer 120 in which the top resist material of theexposed region is not soluble in a developing solution.

According to the present disclosure, the quencher 140 has reducedmobility such that the diffusion through the water drop is substantiallyreduced. In one example, the mobility of the quencher is reduced suchthat the quencher is capable of being leached less than about 10¹³mole/cm² to an immersion fluid during immersion lithography.

In one embodiment as illustrated in FIG. 4, the quencher 140 ischemically bonded to a polymer 160 such that the quencher has a reducedmobility. The polymer 160 becomes soluble in a developing solution afterreacting with acid. The polymer 160 further includes a short chainpolymer, which is soluble to developing solution. The quencher 140 isnot able to diffuse into the water drop, resulting in a limited range ofmobility through a chain movement of the polymer 160 and/or quencher140.

Referring to FIG. 5 a, the quencher 140 may be bonded to a carbon unit162 of the polymer 160 through a nitrogen atom 142 of the quencher. Inthe present embodiment, the nitrogen atom 142 includes an unpairedelectron to neutralize acid or other active component of the resist. Thequencher 140 includes first and second chemical groups 144, 146 such asalkyl groups bonded to the nitrogen atom 142. An alkyl group may includeH, CH3, C2H5, CF3, C2F5, ring type polymer or ring type polymer with itsring end bond to nitrogen atom 142. The first and second chemical groups144 and 146 may alternatively include other chemical groups. In otherexamples, the polymer 160 may include two carbon units 164 in FIG. 5 b,or three carbon units 166 in FIG. 5 c, or even more carbon units bondedto the nitrogen 142 of the quencher. Such carbon structure has multiplecarbon units in chain and provides a certain flexibility to the bondedquencher 140. The polymer may alternatively include other atomic unitsbonded to the quencher 140.

Referring to FIG. 6, in another embodiment, the quencher 140 may bephysically trapped (fully or partially) inside the polymer 160. Thequencher 140 may have a size substantially large compared to an averagemesh size of the network of the polymer 160 so that the quencher 140 isphysically trapped inside. The quencher 140 may alternatively have acertain structural group to enhance physical entanglement. For example,the quencher 140 may include a long tail (a long chain) or a branchedgroup such that the quencher 140 may be physically tangled with ortrapped by the polymer 160. In another embodiment, the quencher 140 mayinclude a ring structure, a long chain, a branched group, orcombinations thereof, to reduce the quencher mobility.

FIGS. 7 a through 7 j illustrates various exemplary structures of thequencher. A quencher in FIG. 7 a includes two alkyl groups and a ringstructure such as a carbon ring. A quencher in FIG. 7 d includes onealkyl group and two ring structures. A quencher in FIG. 7 b includesthree ring structures. A quencher in FIG. 7 c includes two alkyl groupsand one ring structures having an oxygen atom. A quencher in FIG. 7 eincludes two alkyl groups and a long tail such as a carbon chain. Aquencher in FIG. 7 f includes two alkyl groups and a long tail having anoxygen atom. A quencher in FIG. 7 g includes one ring structure havingan oxygen and two long-chain structures. A quencher in FIG. 7 h includestwo alkyl groups and one branched structure having two short tails. Aquencher in FIG. 7 i includes two alkyl groups and one branchedstructure having two long tails. A quencher in FIG. 7 j includes twoalkyl groups and one branched structure having three short tails. Othercombinations may be implemented to tune the mobility of the quencher foroptimized performance.

Referring to FIGS. 8 a and 8 b, in another example, the quencher ishydrophobic and therefore difficult to diffuse to a water drop. Thequencher may include at least one hydrophobic group. For example, thequencher includes a fluoride. The quencher in FIG. 8 a includes threealkyl groups and at least one of them has a fluoride. The quencher inFIG. 8 b includes one alkyl group, one ring having an oxygen, and a lonechain having multiple fluoride.

In another embodiment, water drops left on the resist layer may be acidtreated right after the exposing process. The acid treatment can beimplemented by spraying acid on the resist surface (and/or the waterdrops thereon) through a chemical inlet integral to the immersionlithography system. The pH value of the treated water drops may beadjusted to a value below about 6. Thus, the quencher has a reduced rateof diffusion into the water drop. Furthermore, photo generated acid mayalso have a reduced rate of diffusion to the water drop. The acidtreatment can also diffuse into the resist film and substantiallycompensate the leaching of the photo acid.

In various embodiments, the mobility of the quencher to the water dropon the resist layer is substantially reduced. The watermark effect isalso substantially reduced. Various embodiments may be modified orcombined for optimized resist patterning process.

Referring to FIG. 9, a flowchart of an immersion lithography method 900form a resist pattern as described. The method 900 includes a step 902to form a photo sensitive (resist) layer on a semiconductor wafer. Theresist layer is substantially similar to the resist layer 120 of FIG. 1,where the quencher material has a reduced mobility. The quencher mayhave structures similar to those illustrated in FIGS. 5 a to 5 c, FIGS.7 a to 7 j, and FIGS. 8 a to 7 b, or combinations thereof.

The method 900 further includes a step 904 to expose the resist layer toa radiation energy such as DUV through a photomask and an immersionfluid. The immersion fluid may be DIW or other suitable fluid having ahigh index of reaction and is disposed between the semiconductor waferand lens of an immersion lithography system to implement the method 900.Since the quencher has a reduced mobility, the quencher has a reducedleaching to water drops left on the resist layer after the exposing step904.

The method 900 then proceeds to a step 906 to bake (post exposure bakeor PEB) the resist layer. The baking temperature may range between about80° C. and 150° C. The baking may have a duration of several minutes asan example. The baking step may further include removing water dropsleft on the resist layer.

The method 900 then proceeds to a step 908 to develop the resist layerin a developing solution. The exposed resist regions are substantiallydissolved.

The method 900 may further include a step between the exposing step 904and the baking step 906 to treat the water drops left on the resistlayer so that the water drops will have pH value below 6. Such acidtreated water drops may also neutralize the diffusion of the basequencher to the water drop. This can reduce the impact of the diffusionof the quencher to the exposed resist regions through the water dropsand also reduce the diffusion of the acid from the exposed resistregions into the water drops.

Thus, the present disclosure provide a photoresist material having apolymer that turns soluble to a base solution in response to reactionwith acid. The material includes a photo-acid generator (PAG) thatdecomposes to form acid in response to radiation energy and a quenchercapable of neutralizing acid and having a reduced mobility.

In some embodiments, the quencher includes a concentration greater thanabout 0.5% of the polymer by weight. The quencher may be capable ofbeing leached at an amount less than about 5×10⁻¹³ mole/cm² to animmersion fluid. The immersion fluid may include water. The immersionfluid may include a suitable fluid having an index of refraction (n)higher than 1.44. The quencher may be chemical bonded to the polymer.The polymer may include at least one carbon unit bonded to the quencher.The at least one carbon unit may be bonded to a nitrogen atom of thequencher. The quencher may include a nitrogen atom having an unpairedelectron. The quencher may include at least one ring structure attachedto the nitrogen atom. The quencher may include at least one offour-carbon chain attached to the nitrogen atom. The quencher maycomprise at least four atom units attached to the nitrogen atom of thequencher. The quencher may include at least one branch chain attached tothe nitrogen atom of the quencher. The quencher may be substantiallyhydrophobic. The quencher may include fluoride.

The present disclosure also provides a material having a polymer thatturns soluble to a base solution in response to reaction with acid. Thematerial includes a plurality of photo-acid generators (PAGs) thatdecompose to form acid in response to radiation energy; and a pluralityof quenchers that are capable of neutralizing acid and have a reducedmobility by at least one of:

-   -   being chemically bonded to the polymer;    -   being substantially hydrophobic; and    -   physically trapped in the polymer.

In some embodiments, the plurality of quenchers include a concentrationabout one fourth of a concentration of the plurality of PAGs. Each ofthe plurality of quencher may include a nitrogen atom having oneunpaired electron. Each of the plurality of quencher may include anchemical group bonded to the nitrogen, wherein the chemical group isselected from the group consisting of an alkyl group, a ring structure,a long chain, a branched group, and combinations thereof. The pluralityof quenchers may include a reduced mobility such that the plurality ofquenchers is capable of being leached less than about 5×10⁻¹³ mole/cm²to an immersion fluid. The material may further include a solvent in thepolymer.

The present disclosure also provides a method for immersion lithography.The method includes forming a photo sensitive layer on a substrate, thephoto sensitive layer including: a polymer that turns soluble to a basesolution in response to reaction with acid; a plurality of photo-acidgenerators (PAGs) that decompose to form acid in response to radiationenergy; and a plurality of quenchers capable of neutralizing acid andhaving a reduced mobility. The method includes exposing the photosensitive layer using an immersion lens system; baking the photosensitive layer, the photo sensitive layer being able to leach theplurality of quenchers less than about 5×10⁻¹³ mole/cm² into animmersion fluid; and developing the photo sensitive layer. The methodmay further include an acid treatment such that pH value of water dropson the photo sensitive layer is below 6 after the exposing of the photosensitive layer. In the method, the baking of photo sensitive layer mayinclude removing water drops.

The foregoing has outlined features of several embodiments so that thoseskilled in the art may better understand the detailed description thatfollows. Those skilled in the art should appreciate that they mayreadily use the present disclosure as a basis for designing or modifyingother processes and structures for carrying out the same purposes and/orachieving the same advantages of the embodiments introduced herein.Those skilled in the art should also realize that such equivalentconstructions do not depart from the spirit and scope of the presentdisclosure, and that they may make various changes, substitutions andalterations herein without departing from the spirit and scope of thepresent disclosure.

1. A material for use in immersion lithography, comprising: a polymerthat turns soluble to a base solution in response to reaction with acid;a photo-acid generator (PAG) that decomposes to form an acid in responseto a radiation energy; and a quencher capable of neutralizing acid andhaving a reduced mobility wherein the quencher comprises a concentrationgreater than about 0.5% of the polymer by weight; wherein-the quencheris capable of being leached at an amount less than about 5×10⁻¹³mole/cm² in an immersion fluid used in the immersion lithography,wherein the immersion fluid includes one of water or a fluid having anindex of refraction (n) greater than 1.44; wherein the quencher issubstantially chemically bonded to the polymer and the PAG is notchemically bonded to the polymer; and wherein the quencher includes astructure selected from the group consisting of 1) two alkyl groups anda ring structure having an oxygen atom; 2) one alkyl group and two ringstructures; and 3) three ring structures.
 2. The material of claim 1,wherein the polymer comprises at least one carbon unit bonded to thequencher.
 3. The material of claim 2, wherein the at least one carbonunit is bonded to a nitrogen atom of the quencher.
 4. The material ofclaim 1, wherein the quencher comprises a nitrogen atom having anunpaired electron.
 5. The material of claim 4, wherein the quenchercomprises at least one ring structure attached to the nitrogen atom. 6.The material of claim 4, wherein the quencher comprises at least fouratom units attached to the nitrogen atom of the quencher.
 7. Thematerial of claim 4, wherein the quencher comprises at least one organicgroup attached to the nitrogen atom of the quencher.
 8. The material ofclaim 1, wherein the quencher is substantially hydrophobic.
 9. Thematerial of claim 8, wherein the quencher comprises fluoride.
 10. Thematerial of claim 1, wherein the quencher comprises two alkyl groups anda ring structure having an oxygen atom.
 11. The material of claim 1,wherein the quencher comprises one alkyl group and two ring structures.12. The material of claim 1, wherein the quencher comprises three ringstructures.
 13. The material of claim 1, wherein the quencher comprisesone ring structure having an oxygen atom and two long chain structures,each long chain structure having four to seven carbon atoms.
 14. Amaterial for use in immersion lithography, comprising: a polymer thatturns soluble to a base solution in response to reaction with acid; aplurality of photo-acid generators (PAGs), which are not bonded to thepolymer, and decompose to form acid in response to radiation energy; anda plurality of quenchers that are capable of neutralizing acid, andhaving a reduced mobility by being chemically bonded to the polymer by aside chain having one to three carbon units; wherein the plurality ofquenchers are configured to exhibit the reduced mobility such that thequenchers are capable of being leached at an amount less than about5×10⁻¹³ mole/cm² in an immersion fluid used in the immersionlithography, wherein the plurality of quenchers include structuresselected from the group consisting of 1) two alkyl groups and a ringstructure having an oxygen atom; 2) one alkyl group and two ringstructures; and 3) three ring structures.
 15. The material of claim 14,wherein the plurality of quenchers comprises a concentration of aboutone fourth of a concentration of the plurality of PAGs.
 16. The materialof claim 14, wherein one or more of the plurality of quenchers comprisesa nitrogen atom having one unpaired electron.
 17. The material of claim16, wherein each of the plurality of quenchers comprises an chemicalgroup bonded to the nitrogen, wherein the chemical group is selectedfrom the group consisting of an alkyl group, a ring structure, a longchain, a branched group, and combinations thereof.
 18. The material ofclaim 14, further comprising a solvent in the polymer.
 19. A materialfor use in immersion lithography, comprising: a polymer that turnssoluble to a base solution in response to reaction with acid; aphoto-acid generator (PAG) that decomposes to form an acid in responseto a radiation energy; and a quencher capable of neutralizing acid andhaving a reduced mobility wherein the quencher comprises a concentrationgreater than about 0.5% of the polymer by weight; wherein-the quencheris capable of being leached at an amount less than about 5×10⁻¹³mole/cm² in an immersion fluid used in the immersion lithography,wherein the immersion fluid includes one of water or a fluid having anindex of refraction (n) greater than 1.44; wherein the quencher issubstantially chemically bonded to the polymer and the PAG is notchemically bonded to the polymer; and wherein the quencher includes astructure selected from the group consisting of 1) two alkyl groups anda long chain, the long chain having an oxygen atom and seven carbonatoms; 2) one ring structure having an oxygen atom and two long chainstructures, each long chain structure having four to seven carbon atoms;3) two alkyl groups and one branched structure having two short chains,each short chain having one carbon atom; 4) two alkyl groups and onebranched structure having two long chains, each long chain having fourto seven carbon atoms; and 5) two alkyl groups and one branchedstructure having three short chains, each short chain having one carbonatom.
 20. The material of claim 19, wherein the quencher comprises twoalkyl groups and a long chain, the long chain having an oxygen atom andseven carbon atoms.
 21. The material of claim 19, wherein the quenchercomprises one ring structure having an oxygen atom and two long chainstructures, each long chain structure having four to seven carbon atoms.22. The material of claim 19, wherein the quencher comprises two alkylgroups and one branched structure having two short chains, each shortchain having one carbon atom.
 23. The material of claim 19, wherein thequencher comprises two alkyl groups and one branched structure havingtwo long chains, each long chain having four to seven carbon atoms. 24.The material of claim 19, wherein the quencher comprises two alkylgroups and one branched structure having three short chains, each shortchain having one carbon atom.